Esters of oxyalkylated phenol aldehyde resins with polyhydric alcohol-polybasic carboxy acid-monocarboxy acid esters



Patented Jan. 8, 1952 ENT OFFICE ESTERS OF OXYALKYLATED PHENOL-ALDE- HYDE RESINS WITH POLYHYDRIC ALGO- HOL-POLYBASIC, CARBOXY ACID-MONO- CARBOXY ACID EIS'IFMIS Melvin De Groote, St. Louis, and "Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing.- Application December 10, 1948,-

Serial N0. 64,463

7 Claims. (01.560 20) 7 The present invention is concerned with certain new chemical products, compounds or compositions, having useful applications in various arts. This inventionis a continuation-in-part of our co-pendingapplication, Serial No. 726,216, filed February 3, 1947 and now abandoned. It includes methods or procedures for manufacturme; said new products, compounds or compositions, as well as the products, compounds or compositions themselves. v v

Said new compositions are the resultants of the esterification reaction involving, on the one hand, an acidic ester containing (a) at least one polyhydric alcohol radical; (b) at least one polybasic carboxylic acid' radical; and (c) a plurality of acyloxy radicals, each having 3 to 22 carbon atoms, with the proviso that at least one of said acyloxy radicals is derived from hydroxylated detergent-forming monocar-boxy acid having 8 to 22 carbon atoms, each said polyhydric alcohol radical; being ester-linked with a plurality of groups, each of which groupscontains at least one ofsaid acyloxy radicals, the number of said groups ester-linked to each polyhydric alcohol radical being at least equal in number in each instance to the valency of the polyhydric alcohol radical, so that each polyhydric alcohol radical is free from any uncombined hydroxyl radical directly attached thereto and being additional to the number of such groups ester-linked to any other polyhydric alcohol radical contained in the ester, and at least one of said groups containing a polybasic carboxylic acid radical, and .on the other hand, hydrophile synthetic products; ,said hydrophile synthetic products being, oxyalkyla-j tion products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms :andselected from the class consisting of ethylene oxide, propylene oxide,. butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-suscepsubstituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent radicals having the formula (R10)n, in which R1 is a memberselected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus.

' .Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion; This specific application is described and claimed in our co-pending application, Serial No. 64,457, filed December 10, 1948. See also our co-pending application, Serial No. 64,469, filed December 10, 1948.

The new products are useful as wetting, detergent and levelling agents in the laundry, textile and dyeing. industries; .as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the applicationof asphalt in road building and the tible, fusible, organic solvent-soluble, water-rinsoluble phenol-aldehyde resin; said resin being derived by reaction between a, difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol;

saidresin being formed in thesubstantial absence of trifunctional phenols; said phenol being ofthe formula a in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing Waste Water, and various trade wastes and theilike; as germicides, insecticides, emulsifying agents, as for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc. v

For purpose of convenience what is said hereinafter will be divided into three parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; and Part 3 will be concerned with the preparation of the esters so as to yield the new composition or product which is particularly effective as a demulsifier.

PART 1 As to the preparation of the phenol-aldehyde resins reference is made to our co-pending applications, Serial Nos. 8,730 and 8,731, both filed February 16, 1943 both of which are now abandoned, In, such co-pending applications we described a fusible, organic solvent-soluble, waterinsoluble resin polymer of the formula on on on H r H c O R R I In such idealized representation 11." is a numeral varying from 1 to 13 or even more, provided that the resin is fusible and organic solvent-soluble. R is a hydrocarbon radical having at least land not over 8 carbon atoms. Inthe instantapplicastion R may have as many as 12 carbon atoms, as in the case of a resin obtained froma dodecyb phenol. In the instant invention it may befirst suitable to describe the alkylene oxides employed as reactants, then the aldehydes, and finally =the phenols, for the reason that the latter require a more elaborate description.

The alkylene oxides which maybe used are the alpha-beta oxides having not more than 4 carbon atoms, to wit, the alpha-beta ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, .glycide, and methylglycide.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not morethan 8 carbon atoms is satisfactory, so long as it does not possessv some otherfunctional group or structure which will conflict with the resinification reaction or with the subsequent .oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of theresins is particularly advantangeous. Solid polymers of formaldehyde are more expensive and higheraldehydes are both less reactive, and are more expensive. Further,- more, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difficulties into the resinification-step. Thus acetaldehyde, for example, may undergo analdol condensation, and it and most of the higher aide.- hydes enter into self-resinification when treated use of acid catalysts or alkaline catalysts, or

without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and "amine'sa-re' employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. .The compound hexamethylenetetramineillustrates such a combination. In light of with strong acids or alkalies. On the other hand,

higher aldehydes frequently beneficially affect the solubility and fusibility of .a resin. This is illustrated, for example, by the different characteristics of the resin prepared from para: tertiary amylphenol and formaldehyde on one hand, and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas the latter is soft and tacky, and obvious.- ly easier to handle in the subsequent oxyalkyla: tion procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural re: quires careful control for the reason that in addition to its aldehydic function, furfural can form condensations by virtue of its unsaturated struce ture. The production of resins from furfural for use in preparing products from' the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition :to formaldehyde, are acetaldehyde, propionic aides hyde, butyraldehyde, Z-ethylhexanal, ethylbutyr.v aldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use ofglyoxal should be avoided due to' the'fact that it is tetrafunctional. However, our experience has been-that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resinifi-' these various reactions it becomes diflicult to present any'formula which would depict the struc-' ture of the various resins prior to oxyalkylation. More'will be said subsequently as to the difference between the use of an alkaline catalystand an acid catalyst; even in the use of analkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not'only those-previously enumeratedbut also the hydroxidesof the alkali metals, hydroxides-ofthe alkaline earth metals, salts of strong bases and-weak acids such as sodium acetate, etc.

Sui-table phenolic reactants include the 'following: Para-tertiarybutylphenol; para-secondary butylphenol; para tertiary amylphenol; para-secondary-amylphenol; para-tertiary-hexy-lphenol para-isooctylphenol; ortho -phenylphenol; para-phenyl-phenol; orthp-benzylphen01; para-benzylphenol; we and para-cy'clohexylphenol, and-the corresponding ortho-para substituted metacresols and 3,5-xylenols. Similarly, one may use paraorortho-nonylphenol or a mixture, paraor decylphenol or a, mixture, menthylphenol, or paraor ortho-dodecylphenol.

' The phenols herein contemplated for-reaction may be indicated by the following formula:

in which R isselected fromrthe'. classconsisting of hydrogen atoms and...hydrocarbon radicals havingat least 4 carbon-atoms and not more than 12 carbon atoms, with-the proviso'that one occurrence of R is the hydrocarbon substituent and the other. two occurrences rare hydrogen atoms, and with .the further provision that' one or both of the 3 and 5 positionsmay. be-methyl substituted.

The above formula tpossibly .canbe restated more conveniently. in the followin .xmanner, to wit, that the phenol. employed isof :the' follow.- ing formula, with the proviso that R is at'hydroe carbon substituent located in the 2, 4, .6 position, again with theprovisionsas'to .3 or 3,5' methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginnin with the hydroxyl position as one:

The manufacture of thermoplastic phenolaldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted'by a hydrocarbon group, and particularly by one having at least lJcarbon atoms and not more than 12 carbon atoms, is well known. As has been previously pointed out, there is no objection to a methyl radical provided it is present in the 3 or 5 position.

These resins, used as intermediates to produce the products of the present invention are described in detail in our Patent 2,499,370,.grant-. ed March 7, 1950, and specific examples of suitable resins are those of Examples 10. through 103a of that patent, and reference is made thereto for a description of these intermediate resins and for examples thereof.

PART 2 Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by thefact that it becomes self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. The olefin oxides employed are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide. Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surface-active properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the resin molecule, oxyalkylation may be satisfactorily continued using the more favorable members of the class, to produce the desired, hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more efiective than propylene oxide, and propylene oxide is more effective than butylene oxide.- Hydroxy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more effective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene oxide,

6.. and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the initial reactants used in the practice of the present invention are prepared is advana tageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate. sodium hydroxide, sodium methylate, caustic potash etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room tem-. perature to as high as 200 C. The reaction may be conducted with or Without pressure, i. e., from zero pressure to approximately 200 Or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric acid is used to catalyze the resinification reaction, presumably after being converted into a sulfonic acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and may be .permitted to be present in the final product used as a demulsifier, it is our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain effective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of approximately 2 0r 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be reacted further in theusual manner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resinwin propylene; oxide even .thoughnoxyfilkylae tion is taking vplacelto algreateror lesser degree. After a solution has been. obtained .whichmpresents the. original resindissolved in propylene oxide or butylene oxide, or amixture which ncludesthe oxyalkylated product, ethylene oxid is added to react with .the liquid masseuntil hydrophile properties are obtained- Since-ethylene oxide is more reactive thanpropylene. oxide or butylene oxide, the .final: product; may contain someunreacted. propylene oxide or :butylene oxide which can be eliminatedlbyvolatilization or distillation in any suitable manner.

Attention is directedtothe factthatthe resins herein described must be fusible or soluble .in an organic solvent. Fusibleresins. invariablyare soluble in oneor more organic solventsisuch as those mentioned elsewhere herein. It is .to be emphasized, however, that the organic solvent employed-to indicate or assure that the resin meets this requirement need not be theione used in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and .alcoholeethers. However, where a resin is soluble in an organic solvent, there are usually available other organic solvents which are not susceptible to oxyalkylation, useful forzthe oxyalkylation step. Inany event, the organicsolvent-soluble resin can be finely powdered, 'forlinstance to 10.0 to 200 mesh, and a slurry or suspension prepared in xylene or the like, and subjected-to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified possess reactive .hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with ability to vary thehydrophile properties of the hydroxylated intermediate reactants from minimum hydrophile properties to maximum hydrophile properties. Such properties in turn, of course, are effected subsequently by the acid .employed for esterification and the quantitative nature of the esterification itself, 1. e., whether it is total or partial. .It may be well, however, to point out what has been said elsewhere inregard to the. hydroxylated intermediate reactants. See, for example, our copending applications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948, and Serial No. 42,133, filed August 2,-1948, and Serial ,No; 42,134, filed August 2, 1948, all four ofwhich are, now abandoned. The reason is that the esterification, depending on the acid selected, may vary the hydrophile-hydrophobe balance in one direction or the other, and also invariably causes the development of some property which makes it inherentlydifferent from the two reactantsfrom which the derivative ester is obtained.

Referring to the hydrophile hydroxylated in termediates, even more remarkable and equally diificult to explain, are the versatility and the utility of these compounds considered as chemical reactants as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly asth e point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surface-activity or minimum surfaceactivity means that the product shows at least emulsifying properties or. self-dispersion in cold 8. or..even in warmdistilled water; (if-3."..to 40 'C.) in concentrationsof 9.5% to 5.0%.. .These'materials are generally moresolubleincold water. than warm water, and.may ..even -.be veryinsolnble. in

boiling water. .cMdderately .high temperatures.

aid in reducing; the viscosity oi the ;solute. under examination. csometimes if .one. continues. to shake. a hot solution, even though cloudy .or containing an. insoluble phase, .one. finds. that solution takesplace to give a homogeneous phase as the... mixture cools. Such SGIfrdiSDGISiOIl tests are conducted. in. the .absence ofan; insoluble solvent. 7

When the hydrophilerhydrophobe. balance is above the. indicatedminimum (2 moles of; ethyleneoxide per phenolic .nucleus. orthe .e.quiva-. lent) but .insufiicientto give. a. sol. as,..described immediately preceding, thenand in. that event. hydrophile properties are indicated by the fact that one can produce an emulsion by having present 10% to 50% of an inert solvent. such as xylene. All that one need to do is to have a xylene. solution within the range of 5,0 to parts by weight of oxya-lkylated derivatives and 50 to 10 partsby weight of xylene and mix such solution with one, two. orthree times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be ofthe oil-in-water type or the water-in-oil typeiusually the former) but, in any event, due to the hydrophile-hydrophobe balance oithe ,oxyalkyl-ated derivative. Weprefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test. rather than evaporate thesolvent and em- Ploy any-more. elaboratetests, if the solubility is not sufficient to permit the. simple sol test in water previously noted. I

If the product is, not. readily water. soluble it may be dissolved in ethyl or methyl alcohol, ethyleneglycol diethylether, or diethylene glycol diethylether, with a little. acetone added if required, making a rather concentrated solution, for instance 40%-to-5 (l%, and then, adding enough of the concentrated alcoholic or equivalent solu-' tion to give the previously, suggested 0.5% to 5.0% strength solution, If the product is self-dispersingfti. e., if the oxyalkylated product is a liquid or a liquidsolution self-:emulsifiableLsuch sol or dispersion is referred to asat least semi-stable in the. sense that sols, emulsions, ordispersions prepared are relatively. stable, if they remain at least for someperiod of time, forinstance 30 minutes to two hours,before showingany marked separation. Such tests are conducted at room temperature (22C.). Needless to say, a test can be made in presence, of an insoluble solvent such as 5% to 15% of xylene, as noted in previous ex-' amples. If such mixture, 1. e., containing a waterinsoluble solvent, is :at least semi-stable, obviously the, solvent iree.productwould be even more so. Surf-aceeactivity' representing an advanced hydrophile-hydrophobe balance can also be determinedby the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surface-activity in a material is ,theability toform a permanent foam in dilute aqueous .solution, for example, less than.0.5%, when'inthe higher oxyalkylated stage, and to form an emulsion in the lower and intermediatestages oi oxy kyltion.

Allowance mustbe made for the presence of a solvent in the final product in relation. to the hydrophile properties. of. the final produce. The principle involved in the rnanufacture of the herein contemplated. compounds. for .use as polyhydric as follows: in an equal weight of xylene. Such 50-50 solureactants, is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are self-emulsifying; that is, when shaken with Water they produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent such as xylene, an emulsion. In demulsification, it is sometimes preferable to use a product having markedly enhanced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that with products of the type used herein, most efiicacious results are obtained with products which do not have hydrophile properties beyond the stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against paraflin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably determined in this same manner but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oil-in-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is The oxyalkylated resin is dissolved tion is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sumcient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-inwater type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking v and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1' part phenol to 1.1

formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate theabove emulsification test.

In a few instances, the resin may not be sufiiciently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the" presence or absence of hydrophile or surfaceactive characteristics in the polyhydric reactants used in accordance with this invention. They dissolve or disperse in water; and such dispersions form readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent'waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylenefree resultant may show initial or incipient hydrophile properties, whereas in presence of Xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It'is well known that the size and nature or structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or 7 phenolic nuclei with approximately 4 /2 or 5% nuclei as an average. More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable procedure, particularly by cryoscopic methods;

proportion, combines :but using the same reactants and using more "zdrastic conditions of resinification one usually finds that higher molecular weights are indicated by :higher melting points of the resins-andatendployed in a :first stage, followed by neutralization and addition of a small amount zofracid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst, the number ofmoles of aldehyde, such :as formaldezh ydepmustbe greater thancthe moles of phenol employed inorder to introduce methylol groups :in *thezintermediate stage. There is no indication that-suchgroupsrappear in the final resiniif prepared zbyethe .use of an acid 'catalyst. It is-pos- :sible that-such groups :mayappear in the finished resins prepared solely with an alkaline catalyst; butwezhave never been able to :confirm this fact in :an examination of a large number of resins prepared by ourselves. Our :preference, however, "is to useian acid-catalyzedresin, particularlyemploylng 1a formaldehyde-to-phenol ratio .of 0.95:

to 120 andpas far as we have been able to determine, such resins are free from 'methylol groups. As ;a matter *of fact, it is probable'that inziacid-catalyzed resinifications, the methylol structure may appear only momentarily at the...

very beginning of the reaction-and in all prob- :ability is converted at .once into a more ,complex structure during. the sintermediate stage.

.Gne procedure which can be employed in 'the use of anew-resinrto prepare polyhydric reactants -i for use in the preparation of compounds em- ;ployed in-the present invention, is to determine the :hydroxyl value by the 'Verley-Bolsing method 'oraitsiequivalent. The resin as such, or in the form of a solution as described, is then treated withethylene-oxide :in presence of 0.5% to "2% of sodium methylate as a 'catalystin step-wise :fashion. The conditions of reaction, as far as time or :per cent are concerned, are within the range :previouslywindicated. With suitable agitationtheethylene oxide, if added in molecular within a comparatively short :time, for instance a few minutes to;2 to 6 hours, but -in some instances requires as much as -8 t' 24 hours. Auseful temperature range is from -125-to 225C. Thecompletion of the reaction-of each addition of ethylene'oxide in stepwise iashion is usually indicated by the reductionspr elimination of pressure. An amount-conveniently used for each addition is generally equivalent to :ap-mole or two moles -of ethylene :oxide per :hydroxyl radical. When the :amount "ofeethylene oxide added is equivalent to approximately 50% by weight of the original resin, a :sample' us tested for incipientvhydrophi'le propertiesby simply shaking up in water as is, or after-the-elimination of -the solvent :if a solvent is vpresent. Theamount of ethylene oxide used "to obtain a useful demulsifyi-ng agent as .a rule varies from 70% by weight of'the -original resin to assmuch :as five or six times the weight of the original resin. .In :thecase of a resin derived 'fromapara-tertiary butylphenohas little as 50% "by :weight of ethylene oxide may give suitable solubility. 'With propylene oxide, even a greater which no hyd-roxyl is present.

molecular proportion is required and sometimes arresultant of only limited hydrophile properties isobtainable. The same-is true to even agreater extent with butylene oxide. The hydroxylated :alkylene oxides are more effective in v soluloilizing properties than the "comparable compounds in Attention is directed to the fact that in the subsequent examples reference is made to the step-Wiseaddition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection to the continuous addition of alkylene oxide until the desired stage of reactionis reached; In fact, there ,may be less of a hazard involved and it is often advantageous to =add-the--alkylene oxide slowly in'a continuous stream and in such amount as to avoid exceeding the higher pressures noted in-the various examples or elsewhere.

as acetaldehyde, the resultant is a comparatively soft-orpitch-like resin at vordinary temperatures.

Such resins'become'comparatively "fluid-at 110 to 165 'C. .as a rule, and'thus can be readily oxyalkylated preierably oxyethylated, without the use of a solvent.

What hasbeen said previously is not intended toisuggest "that'any experimentation is--necessary to determine the -degree of oxyalkylation, and particularly oxyethyla-tion. What :has been said previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated :resinsjhaving surface activity-show unusual :prop- --erties=a1s the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhyd-ric- -alcohols in a surface-active or subsurface-active range without examining them by reaction with a number of-the typical esters hereindescribed and subsequently examining the re- 'sultant for utility, either in :demulsification or in some-other-art or industry as referred to else- -where,qor-as-a reactant 'for the manufacture of more complicated derivatives. A few simple laboratory tests which can be conducted in a routine mannerwillusuallygive'all the informa tion that-is-required.

For instance,.-a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyeth- -ylate such (resin, using the following four ratios 'of moles of ethylene oxide per phenolic unit equivalent: 2 to :1; 6 to l; 10 to 1; and 15-130 1. From a sample of each product remove any solvent that may be present, such as "xylene. Prepare 0.5% and 5.0% solutions :in distilled watenaspreviously indicated. A mere examination'of .suchseries-will generallyreveal an approximate range of minimum hydrophile charactern'moderate' hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does :not show -minimum hydrophile character by :test of "the solvent-free product, then one should test its capacity-to form an emulsion when admixed with xylene or other insoluble solvent. If neither test-shows the required minimum hydrophile property, repetition using 2 /2 to 4 moles per-phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 to v1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentrationrange is apermanent trans- .alkylene oxide. care to go to the trouble of calculating molecular 13 lucent sol when viewed in a comparativelythin layer, for instance the depth of a'test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance of xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is anexcellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may require the use of increased amounts of However, if one does not even weights, one can simply arbitrarily prepare compounds containing ethylene oxide equivalent to about 50% to 75% by weight, for example 65% by weight, of the resin to be oxyethylated; a second example using approximately 200% to 306% by weight, and a third example using about 500% to 750% by weight, to explore the-range .of hydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be made by a very simple test using a pilot plant autoclave having a capacity of about to gallons as hereinafter described. Such laboratory-prepared routine compounds can then be tested for solubility and, gen- .erally speaking, this is all that is required to give .a suitable variety covering the hydrophile-hydrophole range. All these tests, as stated, are intended to be routine tests and nothing more.

They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly-arbitrary manner, a series of compounds illustrating the hydrophile-hydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instanceone should know (a) the molecular size, indicating the number of phenolic units; (b) the nature of the aldehydic residue, which is usually CH2; and (c) the nature of the substituent, which is usually butyl, amyl,

0r phenyl. With such information one is in substantially the same position as if one had personally made the resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units of the resin of thefollowing over-simplified formula:

(ll-:1 to 13, or even more) is given approximately by the formula: (Mol. wt.

of phenol 2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would be n times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical proximately by taking (1t 7 2) .times the 14 weight of the internal element; Where, the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculationwill be in error by several per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight,.one need only introduce, for example, two molal weights of ethylene oxide or slightly more, per phenolic nucleus, to produce a product of minimal hydrophile character. Fur- .ther oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a. large number of oxy'ethylated products of thety-pe described herein, we have found no instance where the use of lessthan 2 moles ofethylene oxide per phenolic nucleus gave' desirable products.

Examples 11) through 18b and the tables which appear in columns 51 through 56 of our said Patent 2,499,370 illustrate oxyalkylation products from resins which are useful as intermediates for producingthe esterified products of the present invention, such example giving exact and complete details for carrying out the oxyalkylation procedure. l

The resins, prior to oxyalkylation, vary from tacky, viscous liquids to hard, high-melting solids. Their color varies from a light yellow through amber, to a deep red or even almost black. In the manufacture of resins, particularly hard resins, as the reaction progresses the reaction mass frequently goes through a liquid state to a sub-resinous or semi-resinous state, often characterized by being tacky or sticky, to a final complete resin. As the resin is subjected to oxyalkylation these same physical changes tend to take place in reverse. If one starts with a solid resin, oxyalkylation tends to make it tacky or semi-resinous and further oxyalkylation makes the tackiness disappear and changes the product to a liquid. Thus, as the resin is oxyalkylated it decreases in viscosity, that is, becomes more liquid or changes from'a solidto a liquid, particularly when'it is converted to the'water-dispersible or water-soluble stage. The color of the oxy- ,alkylated derivative is usually considerably lighter than the original product from which it is made, varying from a pale straw color to an amher or reddish amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick viscous sirup. Some products are waxy. vThe presence'of a solvent, such ,as 15% xylene or the like, thins the viscosity considerably and also reduces the color in dilution. No undue significance need, be attached to the color for the reason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared as customarily employed in varnish resin manufac- ,ture, i. e., a procedurejthat excludes the presence ,of oxygen during theresinificationyand.subsequent cooling of thel'resin, then of course the initial resin' is much lighterin color. Wehave employed some resins which initially are almost water-white and also yield a lighter colored final product. l l I Actually, in considering the ratio ofalkylene oxide to add, and we have previously pointed out that this can be predetermined using laboratory tests, it is our actual preference from a practical standpoint to make tests on-a small pilot plant scale. Our reasonfor so doing is that we make one run, and only one, and that we have a complete series which shows the; progressive effect ci -introducin the oxyalkyiati'ng agent; for -in-- stance, the ethyleneoxy radicals-r Our preferred procedure: is as" follows: We prepare a suitable resin, orforthat matter, purchase it in the open market. Weemploy 8- pounds of resin-and 4 pounds of xylene and place the'res'in and xylene in a suitable autoclave= with an open reflux condenser. We prefer to heat'and stir until the solution is complete. We havepointed out that soft resins which are fluid or semifluid can be readily prepared in various ways, such as'the use of ortho-ter-tiary amylphenol, ortho-hydroxydiphenyl, ortho' decylphenol', or by the useof higher molecular weight aldehydes than formaldehydez' If such resins are used, a solvent need not be added but may be added as a matter of convenience or for comparison if desired. We then add a catalyst, for instance, 2% of caustic soda in the form of a to 30% solution, and remove'the water'of solution or formation. We then shut off the reflux condenser and use the equipment as an autoclave'only, and oxyethylate until avtotal of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin. We prefer a temperature of about 150 C. to 175 C. Wealso take samples at intermediate points as indicatedin the following table:

Pounds of Ethylene Oxide Added per 8-p0und Batch Percentages Oxyethylation to 750% can usually be-completed within 30 hours andfrequently more quickly.

The samples taken arerather small, for instance, 2 to 4 ounces, so thatno correction-need be made inregardto the'residual reaction mass. Each sample isdivided in two. One-half the sample is placed in an evaporating dish .on the steam bath overnight so as. to eliminate the x-ylene. Then 1.5% solutions are prepared from both series of samples, 1. e., the series with xylene present and the series withxylene-removedl Mere visual examination of any samples in solution may be sufii'cient t'oindi'catei hydrophile character or surface activity, i. e., the product is soluble, forming a colloidal sol, or'pthe', adueous Solution foams or shows emulsifying, property; All these properties are relatedfthrough adsorption atthe' interface, for example,..a gasliqul'd interface or a liquid-liquid interface. If desired, surface'act'ivity can bemeasured in any one of the usual ways using a DuNouy tensiometer 0r dropping pipette, or any other procedure for measuring interracial tension. Such tests are conventional and requireno further description. compound having sub-surface-activity, and all derived from the same resin and oxyalkylated to a greater extent, i. e., those having a greater proportion of alkylene oxide, are useful for the practice of' this invention.

Another reason why we prefer to usea pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene or metacresol satisfactorily. Previous reference has been meets the fact thatone can conduct a laboratory scale test which will indicate whether or not a resin, although soluble in solvent, Will yield an insoluble rubbery product, i. e., a product which is neither hydrophile nor surface-active, upon oxyethylation, particularly extensive oxyethylation. It is also obvious that one may have a solvent-soluble resin derived from a mixture of phenols having present 1% or 2% of a trifunctional phenol which will resultin an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addition of 2 or 3 moles of the oxyalkylating agent per phenolic nucleus, particularly ethylene'oxide, gives a surface-active product which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable product. It is obvious that this present procedure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

It may be wen to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which wouldnot appear a normally conducted reaction.- Reference'has been made to cross-linking and its effect on solubility and also the fact that, if carried far enough, it causes incipient stringiness,-the'n pronounced stringiness, usually followed by a-semi-rubbery or rubbery stage. Incipient stringiness', or even pronounced stringiness, or even the tendency toward a rubbery stage, is not objectionable so long" as the final-product is still-hydrophile and at least subsurface-active. Such material frequently is best mixed with a polar' solvent, such as alcohol or the like, and preferably an" alcoholic solution is used. The point which we want to make here, however, is thispstringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a 'difunctional' phenol and'an aldehyde produce a non-cross-linked resin molecule and if such moleculeis oxyalkylated so asto introduce a plurality or hydroxyl groups in each molecule,

then and-in that event if subsequent etherification takes place, one isgoing to obtain crosslinking in the same general way that one would obtaincross li'nking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethylene oxide. This may be done in a comparatively short time, for instance, at or C. iii e to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or 5 times as long to introduce an equal amount of ethylene oxide employing the same temperature;"' then etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is tocut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermoplastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as to of xylene. Further oxyalkylation, particularly oxyethylation, may then yield a product which, instead of giving a clear solution as previously, gives a very milky solution suggesting that some marked change has taken place. One explanation of the above change is that the structural unit indicated in the following way. where 811. is a fairly large number, for instance, 10 to 20, decomposes and an oxyalkylated resin representing a lower degree of oxyethylation and a less soluble one, is generated and a cyclic polymer of ethylene oxide is produced, indicated thus:

This fact, of course, presents no difliculty f r the reason that oxyalkylation can be conducted in each instance stepwise, or at a gradual rate, and samples taken at short intervals so as to arrive at a point where optimum surface activity or hydrophile character is obtained if desired; for products for use in the practice of this invention, this is not necessary and, in fact, may be undesirable, i. e., reduce the efiiciency of the product.

We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances, of course, such distribution can not be uniform for the reason that we have not specified that the molecules of ethylene oxide, for example, be added in multiples of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum of two moles of ethylene oxide per phenolic nucleus are added, thi would mean an addition of 10 moles of ethylene oxide, but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, even assuming the most uniform distribution possible,

some of the polyethyleneoxy radicals would contain 3 ethyleneoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce moles of ethylene oxide there is no way to be certain that all chains would have 5 units; there might be some having, for example, 4 and 6 units, or for that matter 3 or 7 units. Nor is there any basis for assuming that the number of molecules of the oxyalkylating agent added to each of the molecules of the resin is the same, or diiferent.

Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions 18 of radicals indicated are to be statistically taken. We have, however, included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any other oxyalkylating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds, and for that matter derivatives of the latter, the following should be noted. In oxyalkylation, any solvent employed should be non-reactive to the alkylene oxide employed. This limitation does not apply to solvents used in cryoscopic determinations for obvious reasons. Attention is directed to the fact that various organic solvents may be employed to verify that the resin is organic solvent-soluble. Such solubility test merely characterizes the res.- in. The particular solvent used in such test may not be suitable for a molecular weight determination and, likewise, the solvent used in determining molecular weight may not be suitable as a solvent duringj oxyalkylation. For solution of the oxyalkylated compounds, or their derivatives a great variety of solvents may be employed, such as alcohols, ether alcohols, cresols, phenols, ketones, esters, etc., alone or with the addition of water. Some of these are mentioned hereafter. We prefer the use of benzene or diphenylamine as a solvent in making cryoscopic measurements. The most satisfactory resins are those which are soluble in xylene or the like, rather than those which are soluble only in some other solvent containing elements other than carbon and hydrogen, for instance, oxygen or chlorine. Such solvents are usually polar, semi-polar, or slightly polar in nature compared with xylene, cymene, etc.

Reference to cryoscopic measurement is concerned with the use of benzene or other suitable compound as a solvent. Such method will show that conventional resins obtained, for example, from para-tertiary amylphenol and formaldehyde in presence of an acid catalyst, will have a molecular weight indicating 3, 4, 5 or somewhat greater number of structural units per molecule. If more drastic conditions of resinification are employed or if such low-stage resin is subjected to a vacuum distillation treatment as previously described, one obtains a resin of a distinctly higher molecular weight. Any molecular weight determination used, whether cryoscopic measurement or otherwise, other than the conventional cryoscopic one employing benzene, should be checked so as to insure that it gives consistent values on such conventional resins as a control. Frequently all that is necessary to make an approximation of the molecular weight range is to make a comparison with the dimer obtainedby chemical combination of two moles agitation markedly influences the time reaction.

In some cases, the change from slow speed agitation, for example, in a laboratory autoclave agitationwith a stirrer operating at a speed of 60 19 to 200 R. P. M., to nig'h peedagitation, with the stirrer operating at 250 to 350 R. P. reduces the time required for oxyalkylation by about one-half to two thirds'. Frequently xylenesoluble products which give insoluble products by procedures employing comparatively slow speed agitation, give suitable hydrophile products when produced by similar procedure but with high speed agitation, as a result, we believe, of the reduction in the time required with consequent elimination or curtailment of opportunity for curing or etnenzauon. Even ifthe formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducingproduction time,- by increasing agitating S'pele Iii large scaleoperations, we have demonstrated that economical manufacturing results fromcontinuous oxya-lkylation; that is, an operation in which the aix iene oxide is continuously fed to the reaction vessel; with high speed agitation, i. e., an agitator operating at 250 to 350 R P. M.- Continuous oxyalk-ylation, other conditions being the same, is more rapid than batch 'oxyalkylation, but the latter is ordinarily more convenient for laborator-y operation.- 1 I Previous reference has been made to the fact that in preparing esters or compounds of the kind herein described, particularly adapted for demulsifieation oi water-in-oil emulsions, and for that matter for other-purposes, one should make a complete exploration of the wide variation inhydrophobe-hydrophile balance as previously referred to. 'It has been stated, furtherrnore,- that this hydrophobe hydrophile balance of the oxyalkylated resins is imparted, as far as the range or variation goes, to a greateror' lesser extent to the herein described derivatives. This means that one employing the present invention should take the choice of the most suitable derivative selected from a number of representative compounds, thus, not only should a variety of resins be prepared exhibiting a variety of oxyalkylations, particularly oxyethylations, but also a variety of derivatives. conveniently in light of what has been said previously. From a practical standpoint, using pilot plant equipment, for instance, an autoclave having acapacity .of approximately three to five gallons. we havemade a single run by appropriate selections in which the molal ratio or resin equivalent to ethylene oxide is one to one, 1 to 5, l to 10, 1 to 15,and l to 20. Furthermore, in making these particular runs we have used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder ofethylene oxide without added nitrogen, provided that the pressure of the ethylene oxide was sufliciently great to pass into the autoclave, or else we have used an arrangement which, in essence, was the equivalent of an ethylene oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary selzer bottle, combined with the means for either weighing the cylinder or measuring the ethylene oxide used volumetrically. Such procedure and arrangement for injecting liquids is, of course, conventional. The following data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five difierent variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop im- This can. be done L inediately if there is any indication that reaction is stopped or, obviously, if reaction is not started at the beginning of the reaction period. since the addition of ethylene oxide is invariably an exothermic reaction, whether or not reaction has taken place can be judged inthe usual manner by observing (0;) temperature rise or drop, if any, (h) amount of cooling water or other means required to dissipate heat of reaction; thus, it there is a temperature drop without the use of cooling water or equivalent, or if. there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature and usually the operating temperature. In other words, by experience we have found that if the initial re actants are raised to the indicated temperature and then if ethylene oxide is added slowly, this temperature is maintained by cooling water until the oxyethylation is complete. We have also indicated the maximum pressure that we obtained or the pressure range. Likewise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one period ends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has been subjected to furthertreatment. All this is apparent by examining the columns headed Starting mix, Mix at end of reaction, Mix which is removed for sample, and Mix which remains as next starter.

The resins employed are prepared in the mandescribed in Examples 1a through 103a of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were prepared in 10 to 1-5-gallon electro-vapor heated synthetic resin pilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and completely described in their Bulletin No. 2087 issued in 1947, with specific reference to Specification No. '71-3965. 7

For convenience, the following tables give the numbers of the examples of our said Patent 2,499,370 in which the preparation of identical resins on laboratory scale are described. It is understood that in the following examples, the change is one with respect to the size of the operation.

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by distillation or vacuum distillation In these continuous experiments the speed of the stirrer in the autoclave was 250 R; P. M;

in examiningthe subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance. /2 to one gallon, one can proceed through the entire molal stage of 1 to 1, to 1 to 20; without remaking at any intermediate stage; This is illustrated'by Example 104a. In other examples we found it desirable to take a larger sample, for instance, a 3-gallon sample, at an intermediate stage As a result it was necessary in such instances to start with a new resin sample in order to prepare sufiicient ox-yethylate'dderivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been previously prepared were by-passed or ignored. This is illustrated in the tables where, obviously, it shows that the starting mix was not removed from a previous sample.

Phenol for resin: Para-tertiary amylphenol Aldehyde for resin: Formaldehyde [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to So oi Patent 2,499,370 but this batch designated 10411.]

Mix Which is Mix Which Re- Starting Mix g ggg Removed for mains as Next Sample Starter Max. Max. Time Pressure, Temp erahrs. Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. s Res- 25 sbi- Reaasbi- Resg? S01- Res- 23,- vent in vent in vent in vent in First Stage Resin to Et0 Molai Ratio 1:1. 14. 15. 75 0 14. 25 15. 75 4.0 3.35 3.65 1.0 10.9 i 12. 1 '3.0 150 K 1 Ex. No. 104b Second Stage Resin to Et0 Molal Ratio 1: 12. 1 3.0 10. 0- 12.1 15.25 3. 77 4. 17 j 5. 31 7. 13 7. 93 9.94 158 8'1 Ex. No. 1055. 0.

Third Stage Resin to EtO.. Molal Ratio 1:10. -7. 13 7. 93 9. 04 7.13 7.93 19. 69 3. 29 3. 68 9. 04 3. 84 4. 25 10. 65 60 178 )4 F8 Ex. No.106b

Fourth Stage Resin to Et0 Molai Ratio 1:15 3. 84 4. 25 10. 05 3. 84 4. 25 16. 15 2.04 2. 21 8. 55 1. 80 2.04 7. 00 220 $6 RS Ex. No. 107b Filth Stage Resin to Et0 Moial Ratio 1:20 1.80 2.04 7.60 1. 80 2.04 10.2 100 )6 Q8 Ex. No.108b;.-

I=Insolub1e. S1=S1ight tendency toward becoming soluble. FS=Fair1y soluble. RS=Readi1y soluble. QS=Quita soluble.

Phenol for resin: Nonylphenol Aldehyde for resin: Formaldehyde [Resin made in pilot plant size batch, approximately 25 pounds, correspondingto 70a of Patent 2,499,370 but this batch designated 109a.]

Mix Whieii is Mix Which Re- Starting Mix figg figg Removed for mains as Next Sam Starter Max. Max. Time Pressure, Temge'rahrs. Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. 1 SOI- Res- 33 SO1- Res- 5 S01- Res- $3 801- Res- 3 ;8- vent in vent in vent in vent in First Stage Resin to EtO Molal Ratio 1:1 15. 0 15.0 0 15. 0 15.0 3 5. 0 5.0 1. 0, 10.0 10. 0 2.0 50 150 1% ST Ex. No. 109b Second Stage Resinto EtO I Molal Ratio 1:5... 10 10 2.0 10 10 9.4 2.72 2.72 2. 56 7.27 7.27 6.86 100 147 2 DT Ex. No. 11017"...

Third Stage Resin to EtO V Mo1a1Ratio1:10 7.27 7. 27 6. 86 7.27 7. 27 13. 7 4.16 4.16 7. 68 3.15 3.15 5. 95 125 1% S Ex. No. 111b Fourth Stage Resin to EtO-- Moiai Ratio 1:15.. 3.15 3.15 5.95 3.15 3.15 8.95 1.05 1.05 2. 95 2.10 2.10 -6.00 220 174 r 2% 8 Ex. No. 1125--- Fifth Stage Resin to EtO Molal Ratio 1 :20" 2. 10 2.10 6. 00 2. 10 2. 10 8. 00 220 183 3% VS Ex. No. 1135 S=So1uble. ST=S1ight tendency toward solubility.

DT=Deflnite tendency toward solubility.

VS very soluble.

Phenol for resin. Para-actylphenol Aldehyde for resin: Formaldehyde -[Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 80 of Patent2,-i99,370 but this batch designated 114m] Mix Which is 1 Mix Which Re- Starting Mix fi'g fi g or Removed. for mains as Next Sample Starter Max. Max. Time Pressure, Temp erahrs Soiu bility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Sol- Res- Egg- Soi- Res- 323 801- Res- 80!- Resggf; vent in vent in vent in vent in First Stage A Resin to EtO... I M0181 Ratio 1;:1 14.2 15.8 0 14.2- 15.8 3.26 .3.1 3.4: 0.75 11. 1. 12.4 12.8 .60 150 1%: NS Ex. N0. 114b.

Second Stage Resin to EtO. M0151 Ratio 1:5 '11.. 1 12.4 2. 5 11. 1 12. 4 12. 5 7.0 7. 82 7.88 .4. 1; 1. 58' 4. 62 100 17-1. 56' SS Ex.No.116b.

Third Stage Resin to EtO I M01211 Ratio 1:10 6.64 7.36 0 6.64 7.36 15.0 4....-- ..s 120- 190 1% 8 Ex. No. 116b.

Fourth Stage Resin to Et0 I Mola'l Ratio 1:1 14.40 4.9 0 4.4 4.0 14.8 400 160 56 V8 Ex. No. 1171)...

Fifth Stage Resin to EtO. MolaLRat'lo 1:20.. 4.1 4.68. 4.6 4.1 4.58 18.52 260 172 34: VS Ex. No. 1181)..-" I

s ssoiuble. NS Not soluble. SS SomeWhat soluble. VS=Very soluble.

[Resin made in pilot; plant size batch, approximately pounds, corresponding to 69 at Patent 2;;99370 but this batch designated 11%.]

Phenol for resi-nz' Menthylphenol Aldehyde for resin: Formaldehyde Mix Which is Mix Which Re- Starting Mix ggg figg tor mains as Ne'xt Starter Max. Max. Time Pressure, 'Temp erahrs. S01ubi1ity r b s. Ifibs. Lbs Ibls. gbs. Lbs x b Ifibs Lbs r b s. r bs. Lbs ture,

o es- 0 es- 0 eso 'esvent in no vent in m0 vent in no vent in Eto Firat Stuqe Resin to EtO-. Mole]. Ratio 1:1. 13.65 16.35 0 13. 16.35 3.0 9.56 11.45 2.1 4.1 1.9 0.9 60 150 1% NB Ex. N0.119b

Second Stage Resin to Et0 M01121 Ratio 1:5... 10 12 0 10 i2 10. 4. 52 5. 42 4.81 5. 48 6. 58 6. 94 140 160 1942 S Ex. N0. 120b Third Stage Resin to EtO Molal Ratio 1:10-. 5. 48 6. 58 5. 94 5. 48 6. 58 10. M 8 Ex. No. 121b.

Fourth Stan:

Resin to EtO. Molal Ratio 1=15.. 4.1 4. 9 0.9 4.1. 4.9 13.15 m 1%: Vs Ex. N0. 122b Fifth Stay:

Resin to EtO. M0151 Ratio 1:20.. 3. 10 3. 72 0.68 3.10 3. 72 13. 43 820 170. $4 VB Ex. No. 123b-..-.

SSo1ub1e.- N S- Not soluble. VS- Very soluble. 1

Phenol for resin: Para-secondary butylphenol Aldehyde for resin: Formaldehyde [Resin made in pilot plant size batch, approximately-25 pounds, corresponding to 2a of Patent 2,499,370 but this batch designated 124d] Mix Which is Mix Which Re- Starting Mix g figg of Removed for mains as Next Sample. Starter Max. Max. Time Pressure, Temp erahrs Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Lbs. Lbs. Lbs. Lbs. Sol- Res- Eto Sol- Res- Eto Sol- Res- Em Sol- Res- Eto vent in vent in vent in vent in First Stage Resin to EtO.. Molal Ratio 1:1 14.45 15. 0 14.45 15. 55 4.25 5. 97 6. 38 1. 75 8.48 9.17 2. 50 150 912 NS Ex. N0. 124b.-.-

Second Stage Resin to Et0.. Molal Ratio 1:5- 8. 48 9. 17 2.50 8.48 9. 17 16.0 5.83 6. 32' 11.05 2. 2.85 4. 95 188 $6 SS Ex. N0. b.

Third Stage Resin to EtO.. Molal Ratio 1:10.. 4.82 5. 18 0 4.82 5. 18 14. 25 400 183 )4 8 Ex. No. 126b-- Fourth Stage Resin to Et0 Molal Ratio 1:15 3.85 4.15 0 3.85 4.15 17.0 120 180 VS Ex. N0. 1275"--.

Fifth Stage Resin to Et0 Molal Ratio 1:20.. 2. 65 2.85 4. 95 2. 65 2.85 15.45 B0 170 5i: VS Ex. N0. 128b S=So1ub1e. NS=Not soluble. SS==Somewhete soluble. VS=Very soluble.

Phenol for resin: Menthyl Aldehyde for resin: Propionaldehyde [Resin made on pilot plant size batch, app -oximately 25 pounds, corresponding to 81a of Patent 2,499,370 but this batch designated 129a.)

Mix Which is Mix Which Re- Starting Mix fi 53 of Removed for mains as Next SampE-r Starter Ma M x. ax. Time Pressure, Temp erahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Lbs. Lbs. Lbs. Lbs. Sol- Res- Eto Sol- Res- Eto Sol- Res- Em Sol- Res- Eto vent in vent in vent in vent in First Stage Resinto EtO.. Molal Ratio 1:l 12. 8 17.2 12.8 17.2 2. 75 4. 25 5. 7 0.95 8. 55 11.50 1.80 110 150 55 Not soluble. Ex. No. 1295"-..

Second Stage Resin to EtO Molal Ratio 1:5 8. 55 11. 50 1.80 8.55 11. 50 9.3 4. 78 6.42 5.2 3. 77 5. 08 4.10 100 170 $6 Somewhat Ex. No. 130b. soluble.

Third Stage Resin to EtO-.. Molal Ratio1:10 3. 77 5.08 4. 10 3. 77 5.08 13.1 100 182 M: Soluble. Ex. No. 1315.....

Fourth Stage Resin to 151130.... Molal Ratlo1:15 5.2 7. 0 5. 2 7.0 17.0 2.10 2. 83 6. 87 200 182 M Very soluble. Ex. No. 132b-.-.

Fifth Stage Resin to Et0 Molal Ratio 1:20-- 2.10 2.83 6. 87 2.10 2.83 9.12 90 D0. Ex. No. 133b Aldehyde for resin: Furfuml [Resin made on pilot plant size batch, approximately pounds, corresponding to 42a of Patent 2,499,370 but this batch designated as 13411.]

Mix Which is Mix Which Re- Starting Mix gg figg of Removed for mains as Next Sample Starter MaX Max Time 1Igressure, 'tlempgrahrs solubllity Lbs. Lbs. Lbs. Lbs. Lbs. Lbs Lbs. Lbs

. Lbs. Lbs. Lbs. Lbs. sol- Res- 801- Res- 801- Res- 801- Resvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to Et0. Molal Ratio 1:1.-- 11.2 18.0 11.2 18.0 3.5 2. 75 4.4 0.85 8. 45 13.6 2.65 120 135 )4; Not soluble. Ex. No. 13417..."

Second Stay 2 Resin to EtO I Molel Ratio 1:5.-. 8. 45 13.6 2. 8.45 13.6 12.65 6.03 8.12 7.55 3.42 5.48 5.10 150 14 Somewhat Ex. No. 135D. soluble.

Third Stage Resin to EtO. Molal K215101210 4. 5 8.0 4. 5 8.0 14.6 2. 45 4.35 7.99 2.05 3.65 6.60 180 163 $5 Soluble. Ex. No. 13612..

Fourth Stage Resin to 10120.... Molal Ratio 1:15.- 3.42 5. 48 5. 10 3.42 5.48 15.10 180 188 34 Very soluble. Ex. N0. 137b...

Fifth Stage Resin to EtO. MolaiRatio 1:20.. 2.05 3.65 6.60 2. 05 3.65 13.35 Do. Ex. N0. 138!) Phenol for resin; M enthyl [Resin made on pilot size batch. approximately 25 pounds, corresponding to 89a of Patent 2,499,370 but this batch designated as 139m] Mix Which is Mix Which Re- Startmg Mix figg i gg of Removed for mains as Next Sample Starter Max Max Time 1gressui e, gemperghrs Solubility 5.5 .m. ure, gb gbs Lbs. Lb Lbs Lbs. Lbs. Lm Lbs. Lbs.

ol es Eto S Res Eto Res- Etc 801- Res- Eto vent m vent in vent in vent in First Stage Resin to 16150.... Molal Ratio 1:1 10.25 17.75 10.25 17.75 2.6 2.65 4.00 0.65 7.6 13.15 1.85 90 150 as Not Ex. No. 139b. soluble.

Second Stave Resin to E tO I Molal Ratio 1:5 7.6 13.15 1.85 7.6 13.15 9. 36 5.2 9. 00 0.40 2.4 4.15 2.95 80 177 96 Somewhat Ex. N o. b.- soluble.

Third Stage 5 53i? 2 91 0 2110 :0 4.22 6.98 4.22 6.98 10.0 Ex. No. 1411:--- 90 165 gamble Fourth Stage 0e aio1:15 .76 6.24 3.76 6.24 13.25 .u-.- Ex. No. 1421:... Y I 100 171 531 31 9.

Fifth Stage B12611i10t0-- 0a a 101220-- 2.4 4.15 2.95 2.4 4. 5 11. Ex. No. Hahn-n 1 7D 90 V; Do.

Phenol for resin: Para-octyl Aldehyde for fesin: Furfural Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a 01 Patent 2,499,370 with 206 parts by weight 01 commercial para-octylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as l44a.]

. Mix Which is Mix which Re Starting Mix gg figg of Removed or mains as Next Sample Starter Max. Max. Time Pressure, Temp erahm Solubility lbls. Ifihs. Lbs 1 .1. 5. Ibs. Lbs 1 .1. 5. Ifibs. Lbs Ibls. Ifibs. Lbs

D 6S- 0 es- 0 BS- 0 9S- vent in Eto vent in Eto vent in Em vent in Eto First Slope Resin to EtO Mola] Ratiol 12.1 18. 6 12. 1 18.6 3.0 5. 38 8. 28 1. 34 6. 72 10. 32 1. 66 80 160 M2 Insoluble. Ex. No. 14417.

Second Stage Slight tend- Resin to EtO ency to Molal Rati01:5 9 25 14. 25 9. 25 14. 26 11.0 3. 73 5. 73 4. 44 6. 52 8.62 6. 56 100 177 942 word he- Ex. No. 145b com i n g soluble. Third Stage Resin to EtO- 7 v v Molal Ratio 1:10-- 6 72 10. 32 1.66 6. 72 10. 32 14. 91 4. 97 7. 62 11. 01 1. 76 2. 70 3. 90 86 182 M Fairly solu- Ex. No. l46b.. ble.

Fourth Stage Resin to Et0- r Molal 1251110136-- 6 62 8.62 6.56 5. 52 8. 52 19.81 100 176 $6 Readily solu- Ex. No. 147b..... ble.

Fifth Stall:

Resin to Et0---. Mela] Ratio 1:20.. 1.76 2. 70 3.90 1. 76 2. 70 8.4 80 160 $4 Quite solu- Ex. No. 148b ble.

Phenol for resin: Para-phony; Aldehyde for resin: Furfural [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a of Patent 2,499,370 vvith 170 parts by weight of commercial paraphenylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 14911.]

Mix Which is Mix Which Re- Starting Mix fig ggg Removed for mains as Next Sample Starter Max M Pressm e, Temp era- Solubility 1 .1. 5. abs. Lbs lbls. abs. Lbs lbls. fib's. Lbs Ibis. gm. Lbs

o eso oso eso esvent in E0 vent in Eto vent in Eto vent in Eto First Stage Resin to Et0. I Molal Ratio 1:1--. }13 9 16.1 13.9 16.7 3.0 3.60 4.25 0.80 10.35 12.45 2.20 100 160 )5 Insoluble. Ex. No. 149b- Second Stage Resin to mom. g fg gj M0181 Ratio 1:5.-. 10. 35 12. 45 2. 10. 12. 12. 20 5.15 6. 19 6. 06 5. 20 6. 26 6.14 183 $5 Ward 801w Ex. No. 1500..."

bility. Third Stage Resin to Et0--.- Molal Ratio 1:10.- 8 10. 7 8. 90 10. 70 10. 0 5. 30 6. 38 11.32 3. 60 4. 32 7. 68 90 103 Ma Fairly solu- Ex. No. 1511)-. ble.

Fourth Stage Resin to EtO Molal Ratio 1:15.- 5 20 6. 26 6.14 5.20 6.26 16.64 171 )6 Readily 80l- Ex. N 0. 152b. uble.

Fifth Stage Resin to EtO- Sample somewhat robbery and gelaggfigfigggff: 3 6o 32 60 32 68 tinouls but fairly s laluble 230 2 Phenol for Main: Pom-nonylp'hi enyl Aldehyde {or resin..- Furjural [Resin :made on pilot plant size hatch, approximately pounds, corresponding :to 88 of Patent 12.499370 but this imtetl designated-M15403 Mix WhiC'd is Mix \Vhich Re- Starting Mix gg figg Removed {or mains 338 Next sample Starter Max Max Time 1 Pressure, Temgerahrs Solubility fLbs. .Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lb Lbs. Lbs.. Lbs I Sol- Resv Sol- Res- 801- Reszj ,Sol- 95- E170 vent in vent in vent in vent.

First Stage Resin to EtO Molal Ratio1:1-- 10. 85 20. 76 10. 86 20. 3.0 2. 57 4.90 0.73 8. 28 15.85 2. 27 100 160 Hi l101ub1e. Ex. No.16.

Second Stag;

li ht Resin to 110- tendency M5181 Ratio 1- 8. 28 15. 2. 27 8. 28 15. 85 11. 77 3. 82 7. 33 5. 45 4. 46 '8. 52 6. 32 100 182 $6 .tDWai'd Ex. Nix-1551)-"... becoming soluble.

Tbirdfltage Resin to 'EtO.

Mo1alRatio1:10.. 5. 11.35 5. 95 11.35 16. 75 3. 38 6. 42 9. 60 2.57 4. 93 7. 25 181 Fairly Ex. N0-156 i 1 soluble Fourth Stage 4. 46 8. 52 6. 32 4.16 8. 52 19.07 90 188 )5 .Beadily :SOlublg.

Fifth Stage Resin to 13150....

Molal Ratio1:20 2. 57 4. 93 7. 26 2. 57 4. 93 14. 50 100 Quite Ex. No. 15.812...- i solubls- [Resin made on pilot plant size batch, approximately 25 pounds, oorre Phenol for resin: Parafihonylphmol Aldehydejor resin: Formaldehyde Starting M1! Mix'at End of Reaction mple Mix Which is Removed for mains as Next Starter Mix Whicli Re- 1 Max.

. Lbs. Solvent :Lbs. Resvent Lbs. Resin Lbs. S01- vent Lbs. Resin Lbs. EtO

Lbs. E1 9 Lbs. Rw Lbs Lbs. Solvent Etd ' Pressure,

Max. Temperature, C.

spending .5 9a 01 Patent 2,499,370 but this batch designated as 1590.]

ag? Solubility First Stqge Resin to EtO. Molal Ratio 1:1... Ex. No

Second Stage Resin to EtO.... Mglal Bgjzio 1:15... Ex. No. 16917.

TbiTdSWW Resin to EtO Molal Ratio Ex. No.--

Fourfll Stage Resin to EtO. Molal Ratio 1:15.. Ex. No

Fifth ,Stage Resin to EtO.

Molal Ratio 1 2o-'. Ex. No. 16Gb...

Insoluble.

Soluble.

l Resin made on pilot plant size batch, approximately 25 pound para-secondary butylphenol replacing 164 parts by Phenol for resin: Peru-secondary butylphenol Aldehyde for resin: Furfural Mix which is Mix Which Restarting Mix at $2 3 Removed for mains as Next eac 1 Sample Starter Max. Max

I Pressure, Temgera- 31 Solubility Islbls. Lbs. ga Ibls. gbs. Lbs Islbls. i bs. Lbs 1 .1. 8. Ifibs.

Res- 1; o es- 0 eso esvent in vent in Eto vent in Eto vent in Eto First Stave Resin to EtO M0121 Ratio 1 12.0 17.9 12. 0 17. 9 3. 2. 65 3. 98 0.77 9. 13. 92 2. 73 150 171 $6 Insoluble. Ex. No. 161b Second Stone Slight tend- Resm to-EtO ency to- Molal Ratio 1 9.35 13.92 2. 73 9.35 13.92 13.23 5.00 7. 42 7.08 4. 35 6. 6.15 100 192 }& ward be- Ex. No. 162b. coming soluble. Third Stage Resin to 16150.. M0181 Ratio 11 6. 25 8. 95 6. 25 8. 95 17. 0 3. 23 4. 61 8. 76 3. 02 4. 34 8. 24 120 188 942 Fairly solu- Ex. No. 163b ble.

Fourth Stage Resin to EtO.. M0131 Ratio 1.1 4.35 6. 50 6.15 4.35 6.50 18. 40 100 181 )6 Readily. s01- Ex. No. 16411"-.. uble.

Fifth Stage Resin to EtO. Sample somewhat rubbery and gelat- Molal Ratio 1 0 3.02 4. 34 8. 24 3. 02 4.34 16. 49 inous but shows limited water sol- 120 161 34 Ex. No. 165bubility. I I I [Resin made on pilot plant size batch, approximately 25 pounds, corres para-octylphenol replacing 164 pa Phenol for resin: Pard-octylphenol Aldehyde for resin: Propionaldehyde ponding to 34a of Patent- 2,499,370 with 206 parts by weight of commercial rts by weight of para-tertiary amylphenol but this batch designated as 16641.]

Mix Which is Mix Which Re- Starting Mix figg figg of Removed for mains as Nexl;v

. Sample Starter Max. Max. Time llrgressure, gemp erahrs Solubility 5. sq. m. ure Y vent Eto vent; in Eto vent in Eto vent in Eto First Stage Resin to Et0 Molal Ratio l:1 13. 3 16. 9 13. 3 16. 9 3. O 3.1 4.0 0. 10. 2 12. 9 2.3 100 150 $5 Indoluble. Ex. No. 166b Second Stage Resin to EtO1- M0131 Ratio 1:5--. 10.2 12. 9 2.3 10.2 12. 9 11.3 6. 34 8. 03 7. 03 3. 86 4. 87 4. 27 100 166 )4 B ecoming Ex. N 0. 167b soluble.

Third Stage Resin to 13110.... Molal Ratio 1:113. 6. 46 8. 24 6. 46 8. 24 16. 5 3. 52 4. 49 8. 99 2. 94 3. 7. 51 177 V4 Fairly Solu- Ex. No. 1680..... ble.

Fourlh Stan:

Resin to EtO- Molal Ratio 1:15.. 3. 86 4. 87 4. 27 3. 86 4. 87 13. 02 80 204 $4 Readily sol- Ex. No. 169b...- uble.

Fifth St...

R i 1t EtO .u 1 Molal Ratio1:20 2.94 3.75 7.51 2. 94 3. 75 13.26 V4 Soluble. Ex.'No.170b-.

Phenol for'resin: Para-nonylphenol Aldehyde for'resin: Propionaldehyde [Resin madeon pilot plant size batch, approximately 25 pounds, corresponding to 82a of Patent 2,499,370'but this 'bateh-designatedas 1710.]

- Mix Which is Mix Which Re- Starting Mix fig figg Removerii'or mains as Next Sample Starter Max 'Iirne Pressure, Temp erahrs. Solubility Lbs.. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. 'Lbs. ture' Sol- Res- 'So1- Res: -Sol- Res-, .Sol- Res vent in vent: in went- ;in ventin "First Stage ResintoEtO... Molal Ratio 1: 1... 10. 9 18. 0 10. 9 18. O 3. 0 2. 65 4. 4 0. 75 8. 25 13. 60 2. 25 120 150 M2 Insoluble. Ex. N0. 17lb-.... 1 I

Second Stage EResin-to EtO. V Moial iRatio'qlz5... 8. 25 13. 60 2. 25 8. 25 13. 60 11. 50 5. 8. 35 7. 05 3. 5. 4. 95 174 )6 Becoming Ex. No. 1720. 1 soluble ThiniStane Resin to EtO. Molal Ratio 1:10.. 5. 9. 35 5. 65 9. 35 15. 3. 71 6. 14 10. 35 1. 94 3. 21 5. 40 90 182 FAQ Fairly Ex. N05173b. soluble.

Fourth Stage Resin to EtO- Molal Ratio 1:15.- 3. 15 5. 25 4. 45 3. 15 5. 25 13. 45 182 7% Readily (Ex. No.-.174b. soluble.

Fifth Stage Resin to Et0.. Y M0131 Ratio 1:20.- 1. 94 3. 21 5. 40 1.3 94 33.21 10:65 150 k6 Soluble. Ex. 51.0-1751)..."

Phenol for resin: Para-tertiary amylphenol Aldehyde for resin: Propionaldehyde [Resin made on pilot plantsize hatchapproximately 25 pounds, corresponding to 34a of Patent 2,499,370 but this batch designated as 17611.]

. 'Mix Which is Mix Which Re- Starting -Mix figg figg 'Removed for mainsas Next Sample Starter Max. Max. Time Pressure, Temp erahrs Solubility lbls. abs. Lbs Ibls. 55. Lbs I b s. Ibs. Lb :r b s. gbsf- 50- --es- -0- es-' 0- es-" 0- esvent, in Eco vent .in Em vent .in Eto went .in Eto First Stage .ResintoEtoun Molal Ratio 1: 12. 6 16. 2 12. 6 16. 2 3. 5 3. 08 3. 96 0. 86 9. 52 12. 24 2. 64 M2 Insoluble. Ex. No. 1765..... I

Second Stage I Resin to EtO 1 Molal Ratio 1:5. 9. 52 12.24 2. 64 9. 52 12. 24 12.89 5. 27 (l. 79 7. 14 4. 25 5. 45 5. 75 85 171 B e c 0 min g Ex. No.177b....- --so1u Third Stage Resin=to'2f3t0.... Molal Ratio 1:10.. 6. 5 8. 3 6. 5 8. 3 17. 75 3. 81 4. 87 10. 42 2. 69 3. 43 7. 33 120 183 ,4; Fairly solu- Ex. No. 178b ble.

Fourth Stage Resin to'EtO v 4 Molal Ratio 1:15.. 4. 25 5. 45 6. 75 4. 25 5. 45 17. 25 85 196 $6 Readily sol- Ex. N0. 1795..... uble.

Fifth Stage Resin'to EtQ.... Molal Ratio1:20-- 2. 69 3. 43 7. 33 2. 69 3. 43 14. 55 95 $6 Soluble. Ex. No. 18017.--

detergent-forming acids .resin acids, petroleum acids, etc.

37 PART 3 which the detergent-forming acid and the polycarboxy acid are already present in the form of resulting radicals. Although one may use a tricarboxy acid such as tricarballylic acid, or citric acid, our preference is to employ a dicarboxy acid or acid anhydride, such as oxalic acid, maleic acid, tartaric acid, citraconic acid, phthal- -ic acid, adipic acid, succinic acid, azelaic aid,

sebac acid, adduct acids obtained by reaction between maleic anhydride, citraconic anhydride, and butadiene, diglycollic acid or cyclopentadiene. Oxalic acid is not quite as satisfactory as some of the other acids, due to its excessive decomposition. In light of raw material costs, it

is our preference to use phthalic anhydride, maleic anhydride, citraconic anhydride, diglycollic acid, adipic acid, and certain other acids in the same price range which are both cheap and heat-resistant. One may also use adduct acids of the diene or Clocker type having more than 10 carbon atoms, but those reactants having l carbon atoms or less are definitely preferred.

It is well known that certain monocarboxy organic acids containing 8 carbon atoms or more, and not more than 32 carbon atoms, are characterized by the fact that they combine with alkali to produce soap or soap-like materials. These include fatty acids, For the sake of convenience, these acids will be indicated by the formula R.COOH. Certain derivatives of detergent-forming acids react with alkali to produce soap or soap-like materials, and are the obvious equivalent of the unchanged or unmodified detergent-forming acids. For instance, instead of fatty acids one might employ the chlorinated fatty acids. Instead of the resin :acids, one might employ the hydrogenated resin acids. Instead of naphthenic acids, one might employ brominated naphthenic acids, etc.

The fatty acids are of the type commonly referred to as higher fatty acids; and, of course, this is also true in regard to derivatives which are obtained from higher fatty acids. The petroleum acids include not only naturallyoccurring naphthenic acids, but also acids obtained by the oxidation of wax, paraflln, etc. Such acids may have as many as 32 carbon atoms. For instance, see U. S. Patent No. 2,242,837, dated May 20, 1941, to Shields.

The monocarboxy detergent-forming esters of the oxyalkylated derivatives herein described are preferably derived from unsaturated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include oleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. One may employ mixed fatty acids as, for example, the

fatty acids obtained from hydrolysis of cottonseed oil, soyabean oil, etc. It is our ultimate preference that the esters of the kind herein contemplated be derived from unsaturated fatty acids, and more especially, unsaturated fatty acids which have been subjected to oxidation. In addition to synthetic carboxy acids obtained by the oxidation of paraffins or the like, there is the somewhat analogous class obtained by treating carbon dioxide or carbon monoxide, in the presence of hydrogen or an olefine, with steam, or by causing ahalogenated hydrocarbon isas follows:

acids; and another analogous class actually suitable is the mixture of carboxylic acids obtained by the alkali treatment of alcohols of high molecular weight formed in the catalytic hydrogenation of carbon monoxide.

As is well known, one need not use the high molal carboxy acid, such as a fatty acid, for introduction of the acyl group or acyloxy group. Any suitable functional equivalent such as the acyl halide, the anhydride, ester, amide, etc., may be employed.

- Such polycarboxy reactants and such detergent-forming monocarboxy acids alone or in combination with an appropriate alcohol radical which may be monohydric or polyhydric, have been combined to give suitable reactants for combination with the polyhydroxylated compounds previously described. A particularly suitable type of polycarboxy detergent-forming monocarboxy compound is described in U. S.

Patent No. 2,343,427, dated March '7, 1944, to Wells and De Groote, and is the identical type herein contemplated, except that in the instant case the detergent-forming acid is limited to those having '32 carbon instead of 38 carbon atoms. Thus, the reactant employed for combination with the oxyalkylated resin, in the words of the aforementioned U. S. Patent No. 2,343,427, an ester containing (a) at least one polyhydric alcohol radical, (b) at least one polybasic carboxylic acid radical, and (c) a plurality of acyloxy radicals, each having 8 to 38 carbon atoms derived from any detergent-forming monocarboxy acid having 8 to 38 carbon atoms, with the proviso that at least one of said acyloxy radicals is derived from an hydroxylated detergent-forming monocarboxy acid having 8 to 38 carbon atoms, each said polyhydric alcohol radical being ester-linked with a plurality of groups, each of which groups contains at least one of said acyloxy radicals, the number of said groups ester-linked to each polyhydric alcohol radical being at least equal in number in each instance to the valency of the polyhydric alcohol radical, so that each polyhydric alcohol radical is free from any uncombined hydroxyl radical directly attached thereto and being additional to the number of such groupsester-linked to any other polyhydric alcohol radical contained in the ester, and at least one of said groups containing a polybasic carboxylic acid radical. It is to be noted that such reactant is acidic in nature, due to the presence of a free carboxyl radical, and thus, capable of reacting with the hydroxylated oxyalkylated reactant.

In order to avoid repetition, reference is made to said aforementioned U. S. Patent No. 2,343,427, as to the manufacture of the acidic polycarboxy detergent-forming monocarboxy compound, as if the same text appeared herein. For convenience of comparison the same examples are herein included.

Example 10 Our preferred intermediate reactant is a particularly suitable ester product and its manufacture from phthalic anhydride and castor oil will be described. As a suitable polybasic carboxy acid, phthalic anhydride or phthalic acid is preasansso Castor oil is preferred, because the hydroxylated iattyacid radical .is esterified with the glycerol .radical and the esterificationreaction, therefore, can readily be controlled. Moreover, castor oil .isreadily available ina suitably pure state.

One-pound mole of triricinolein (in the form of vcastor oil which ordinarily contains approximately 85% to 95% triricinolein) is-reacted'with 2 pound moles of .phthalic anhydride .to ,pro-

.duce a mixture .of'acid phthalates consisting essentially of triricinolein dibasic ,phthalate and triricino-lein tribasic phthalate. The reaction vmay be caused to .occur by heating the mixed .materials at a temperatureofapproximately 120 to .1.40 C. for approximately-6 to 12 hours. The

.reaction can be followed roughly by withdrawing a'small sample of the partially reactedmassand permitting it to cool on a watch crystal. When the'reaction has become completed, no crystals .of phthalic anhydrideappear. When the sample no longer shows the presence of such crystals on cooling, it can be titrated with'astandard volu- .-metr-ic alkaline solution so asto indicate-"thatthe acid which remains is due entirely to carboxylic .hydrogen and not to any unreacted :phthalic anvhydride. If care is taken not to use-toohigh temperatures which heterocyclic bodies of the character :above :re-

would cause formation of ferred to, one can dependupon the standard alkaline solution .to indicate the disappearance of the phthalic anhydride. It is not to be inferred,

vhowever, that any cyclic bodies if formed would be unsuitable.

Example 'Maleic acid or anhydride is substituted for p'hth'alic anhydride in precedinglilxample "-10 to "give the corresponding maleic acid derivative,

that is, trir'icino'lein dibasic maleate and tri- "ricinolein tribasic maleate.

I Example i3c .Adipic acid or anhydride is substituted for jphthalic anhydride in preceding Example 10 to give the corresponding vadipic acid derivative,

that is, triricinolein -dibasic adipate and atriricinolein .tribasic adipate.

Example 4c Succ'inic acid or anhydride'is substituted for inolein 'tribasic :succinate.

Example 50 The neutral ester derived 'from'ricinoleic acid and ethylene "glycol, that .is, ethylene glycol diricinoleate, is substituted for triricinoleininpreceding Examples 1 to 4, inclusive, and therati'o'of dibasic acid changed'soas to correspond to one and one-half pound moles or a dibasic acid "Dr or anhydride for each pound moleof ethylene glycol diricinoleate.

The products of the 'esterili'cation produced according to Examples 1c to 50 are viscous, yellowish oily material, resembling somewhat blown caster oil consistency. They are only slightly soluble in either water or in parafiin base mineral oil (not more than one part'to 1000) but'go .into solution with lower'alcohols (methyl to 'octyl) to products described in "the aforementioned U. B. 7

Patent No. 2,343,427 have an acid value, .for'instance, of atleas't'f: 'to 10 as a-mininium. 7

Having obtained the oxyalkylated derivative and the acidic polycarboxy reactant above described, it is only necessary to mix the two rea'ctantsin a'jpr'ede'termined proportion and then cause "esterifi'cation to "take place. Needless to say, 'esterifica'tion may also be accompanied .by rearrangement or cros's-esterification to'some degree. Generally :speaking, ifthe two reactants are mixedandheate'd at a temperatureabovethe boiling point of water and below the pyrolyti'c ,1point, esterifi'cation takes place easily'and'readi- 1y. For ex'ampe, a'temperature of '1'20C.to'2'00 "C. may be employed. If need be, a temperature as high as 250 C. can beemployedprovided it'is :short of the pyrolytic .point. If desired, the reaction can be hastened by the addition of a suitable catalyst, such as paratoluene :sulfonic acid. The'arnount"added maybe in the neigh- "borhood of one-half of 1%; Thereaction also can be "hastened by passing dried "hydrochloric acid gas through the reaction mixture. Thereaction is also 'hastene'd'by' passing any dried inert gas through the mixture, for instance, dried COz ordried nitrogen gas.

One of the easiest and simplest ways of handing the reaction is'to'conductthe'esterific'a- 'tion in presence of an inert waterinsoluble solvent, such as benzene, toluene, xylene,-cymene, decalin, etc. Our" preference is to use xyleneor cymene, 'ior the reason that the-reflux temperatureis usually more than sufficient and 'i's high 'enough'to expedite the=elimination of water. The vapors are ledto the conventional-condenser with the reflux trap which diverts the water and returns the solven't. 'These details willbe-amplifi'ed somewhat in succeeding examples.

.Eztample 1d without determination, based :on the hydroxyl value and weight of the phenol-aldehyde resin originally employed, plus the increase (in weight afteroxyalkylation. -If glycideor methylglycide were employed, allowance would have to be made for .the polyhydric characterof theoxyalkylating agent. .In any -event, if desired, the .hydroxyl value of the oxyalkylated derivative could. be .determined 'by the verley-Bolsing method, or by any other acceptable procedure. Similarly, the acidic value of the acidic reactant was determined by the usual volumetric titration "procedure. Our preferred acidic reactant isv the Jone described under thehe'ading ofExample 1 0. 30mpreferencefis to titrate 'thejproduct to determine its acid value. Based on the known 'hyitlroxyl value of the oxyalkylated derivative and 'thegac'id valueof the jpolycarboxy reactant, it .is' our preference to combine such reactants "in various ratios :so 'a'slto add enough of ".the ,p'olycarb'oxy reactan'tto combine with A, /1,, orflall'thetheoretica l hydroxyl of the oxyalkyla'ted derivatives. As "an example, "an average hydroxyl'va'lue "for the 'hydroxylated derivatives. exemplified'iby Example 12512 is '105; An average 'carb'oxy value for "the 

1. THE RESULTANT OF THE ESTERIFICATION REACTION INVOLVING ON THE ONE HAND AN ACIDIC ESTER CONTAINING (A) AT LEAST ONE POLYHYDRIC NOT MORE CAL OF A POLYHYDRIC ALCOHOL HAVING NOT MORE THAN 6 CARBON ATOMS AND CONTAINING ONLY CARBON, HYDROGEN AND OXYGEN; (B) AT LEAST ONE POLYBASIC CARBOXYLIC ACID RADICAL; AND (C) A PLURALITY OF ACYLOXY RADICALS, EACH HAVING 8 TO 22 CARBON ATOMS DERIVED FROM ANY DETERGENT-FORMING MONOCARBOXY ACID HAVING 8 TO 22 CARBON ATOMS, WITH THE PROVISO THAT AT LEAST ONE OF SAID ACYLOCY RADICALS IS DERIVED FROM HYDROXYLATED DETERGENTFORMING MONOCARBOXY ACID HAVING 8 TO 22 CARBON ATOMS, EACH SAID POLYHYDRIC ALCOHOL RADICAL BEING ESTER-LINKED WITH A PLURALITY OF GROUPS, EACH OF WHICH GROUPS CONTAINS AT LEAST ONE OF SAID ACYLOXY RADICALS, THE NUMBER OF SAID GROUPS ESTERLINKED TO EACH POLYHYDRIC ALCOHOL RADICAL BEING AT LEAST EQUAL IN NUMBER IN EACH INSTANCE TO THE VALENCY OF THE POLYHYDRIC ALCOHOL RADICAL, SO THAT EACH POLYHYDRIC ALCOHOL RADICAL IS FREE FROM ANY UNCOMBINED HYDROXYL RADICAL DIRECTLY ATTACHED THERETO AND AT LEAST ONE OF SAID GROUPS CONTAINING A POLYBASIC CARBOXYL ACID RADICAL LINKED THERETO BY AN ESTER LINKAGE; AND ON THE OTHER HAND HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATIONSUSCEPTIBLE FUSIBLE, ORGANIC SOLVENT-SOLUBLE WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 